DIPYRIDYLATE AND PHENANTHROLINATE COMPLEXES OF LANTHANIDES WITH N,N'-TETRAETHYL-N''-TRICHLOROACETYLPHOS-PHOTRIAMIDE AND DIMETHOXYTRICHLOROACETYLAMIDOPHOSPHATE

V.A. Trush, V. A. Ovchynnikov, V. M. Amirkhanov, V.V. Skopenko.

Department of Inorganic Chemistry, Kiev University, Vladimirskaya St. 64, Kiev 252033, Ukraine

Keywords: carbacylamidophosphates, X-Ray diffraction, lanthanides, ,-dipyridyl, 1,10-phenanthroline.

The coordination compounds of lanthanides with N,N'-tetraethyl-N''-trichloroacetylphosphotriamide (HL') of general formula LnL'3 were reported in []. They are able to attach one or two neutral ligands. The crystalline complexes of the composition Na[LnL''4] were known (L''=dimethoxytrichloroacetylamidophosphate-anion) [], while the LnL''3 complexes were not obtained in the crystalline form.

This work deals with the results of investigation of dipyridylate and phenanthrolinate Ln(III)-complexes with N,N'-tetraethyl-N''-trichloroacetylphospho-triamide (HL') and dimethoxytrichloroacetylamidophosphate (HL'') of the general formula LnL'3Dipy, LnL'3Phen, and LnL''3Dipy, LnL''3Phen, where Dipy = (,-dipyridyl and Phen = 1,10-phenanthroline.

The compounds were studied by means of IR, NMR and electronic spectroscopy. AuL'3Dipy and SmL''3Phen structures were studied by X-Ray analyses.

According to the X-Ray diffraction, the obtained complexes in the each of above mentioned rows are isostructural crystalline compounds.

The coordination type of the ligand and the nearest environment of the central ion were determined. The above mentioned ligands are coordinated in bidentate manner via the oxygen atoms of phosphoryl and carbonyl groups in the deprotonated form. The planar molecules of a,a'-dipyridyl and 1,10-phenanthroline form five-membered chelate rings. Coordination number of the central atoms is equal 8 in both cases.

On the basis of X-Ray structural data the comparative analysis of the free ligand's geometry and complexes have been done.

 

  1. V.V.Skopenko, V.M.Amirkhanov, V.A.Ovchinnikov, A.V.Ourov, Russian Journal of Inorganic Chemistry 41, No 4 (1996) 589-594.
  2. V.M.Amirkhanov, V.A.Trush, A.A.Kapshuk, V.V.Skopenko, Russian Journal of Inorganic Chemistry 41, No 12 (1996) 1947-1952.